Linear and Nonlinear Optical Properties from TDOMP2 Theory

We present a derivation of real-time (RT) timeand its biorthogonal companion, time-dependent non-orthogonal OMP2 theory, starting from the time-dependent bivariational principle and a parametrization based on the exponential orbitalrotation operator formulation commonly used in the timeindependent molecular electronic structure theory. We apply the TDOMP2 method to extract absorption spectra and frequencydependent polarizabilities and first hyperpolarizabilities from RT simulations, comparing the results with those obtained from conventional time-dependent coupled-cluster singles and doubles (TDCCSD) simulations and from its second-order approximation, TDCC2. We also compare our results with those from CCSD and CC2 linear and quadratic response theories. Our results indicate that while TDOMP2 absorption spectra are of the same quality as TDCC2 spectra, including core excitations where optimized orbitals might be particularly important, frequency-dependent polarizabilities and hyperpolarizabilities from TDOMP2 simulations are significantly closer to TDCCSD results than those from TDCC2 simulations.